Preparation of highly basic alkylphenates and sulfurized alkyphenates

ABSTRACT

Process for preparing highly basic alkaline earth metal alkylphenates or sulfurized alkylphenates wherein the process comprises: A. FORMING AN ADMIXTURE OF ALKYLPHENOL OR SULFURIZED ALKYLPHENOL, NONVOLATILE DILUENT OIL, VOLATILE PROCESS SOLVENT AND WATER, B. ADDING AN OVERBASING AMOUNT OF ALKALINE EARTH METAL IN A GLYCOL ETHER AT A TEMPERATURE FROM ABOUT 20* TO ABOUT 55* C., c. adding a neutralizing amount of alkaline earth metal in a glycol ether at a temperature of about 55* to about 100* C., and D. REMOVING THE VOLATILE MATERIALS BY HEATING. The products are useful as additive agents for lubricating oils.

Rogers et al.

[ PREPARATION OF HIGHLY BASIC ALKYLPHENATES AND SULFURIZED ALKYPHENATES [75] Inventors: Lynn C. Rogers; Mack W. Hunt,

both of Ponca City, Okla.

[73] Assignee: Continental Oil Company, Ponca City, Okla.

[22] Filed: May 17, 1971 211 Appl. No.: 148,262

[52] US. Cl. 252/417, 252/18 [51] Int. Cl. Cl0m l/40, Cl0m 1/38 [58] Field of Search 252/427, 18;

[56] I References Cited UNITED STATES PATENTS 3,474,035 10/1969 Dadura 252/427 3,350,310 10/1967 Herd et al 252/42] 3,493,516 2/1970 Allphin et a1 252/42.7 X

2,788,325 4/1957 Meyers et a1. 252/427 2,808,377 10/1957 Davidson et al..... 252/427 3,388,063 6/1968 Allphin 252/42.7 X

3,336,224 8/1967 Allphin 252/427 1 Aug. 28, 1973 Primary Examiner-Daniel E. Wyman Assistant Examiner-W. Cannon Attorney-Joseph C. Kotarski, Henry H. Huth, Robert B. Coleman, Jr., Bayless E. Rutherford, Jr. and Kemon, Palmer & Estabrook [57] ABSTRACT Process for preparing highly basic alkaline earth metal alkylphenates or sulfurized alkylphenates wherein the process comprises:

a. forming an admixture of alkylphenol or sulfurized alkylphenol, nonvolatile diluent oil, volatile process solvent and water,

b. adding an overbasing amount of alkaline earth metal in a glycol ether at a temperature from about 20 to about 55 C.,

1 PREPARATION OF HIGHLY BASIC ALKYLPIIENATES AND SULFURIZED ALKYPIIENATES BACKGROUND The use of alkaline earth metal salts of both alkylphenates and sulfurized alkylphenates as additives for lubricating oilshas been known for many years, Lubricating oils containing these materials can be used ineither internal combustion engines or diesel engines. The presence of these materials in the lubricatingoils improves the detergency characteristics; reduces engine wear, minimizes the formation of harmful deposits on engine parts, and improves the resistance'of the oil to oxidation.

Still further, the use of highly basic alkaline earth metal salts of alkylphenates or sulfurized alkylphenates as additives in lubricating oils has been known for several years. The term highly basicrefers to materials containing an excess of alkaline earthmetal basic compounds over the amount of alkaline earth-metal required to neutralize the alkylphenol or sulfurized alkylphenol. The presence of these, basic alkalineearth metal compounds serves to neutralize acidic cmpounds formed during combustion of the fuel used.

The present invention is concerned with'an improved 2 3,350,310; 3,367,867; 3,372,l l6; and 3,474,035. Inasmuch as the latter-mentioned patents are considered to be even less pertinent than the ones discussed, it is not believed necessary to provide any discussion of them herein.

BRIEF SUMMARY OF THE INVENTION Broadly stated, the present invention concerns a pro cessfor preparing highly basic magnesium, calcium or barium salts of alkylphenols or sulfurized alkylphenols, wherein the process comprises the steps of:

a. forming an admixture of alkylphenol or sulfurized alkylphenol, nonvolatile diluent oil, volatile process solvent and water,

b. adding to the admixture of step (a) an overbasing amountof magnesium, calcium or barium in a glycol ether at a temperature of to about 55 C.,

process for preparing highly basic alkaline earth metal alkylphenates or sulfurized alkylphenates; It is particularly concerned with the preparation of magnesium alkylphenates, or sulfurized alkylphenates, containing a large amount of dispersed magnesium compounds, usually as the carbonate, hydroxide or mixturesthereofi' PRIOR ART As a result of a prior art search the following references are considered to be the most pertinent.

U.S. Pat. No. 2,788,325 teaches the use ofmagnesium alkoxy alkoxides to prepare neutral magnesium phenates. The patent teaches the use of temperatures between 100 C. and 250 C. and-substantially anhydrous conditions. US. Pat. No. 2,808,377 teaches a process for preparing neutralized alkaline earth metal alkylphenolsultides. The process uses a pre-treatmentstep wherein from 3 to 5 percent of the amount of alkaline earth metal base required to neutralize the alkylphenol sulfide is used. The temperature in the pre-treatment step is ll60 F. (54-7l C.). A small amount of water is present during the pre-treatrnent step (0.8-l0.0 percent by weight based on alkylphenol sulfide). Following the pre-treatment step a neutralizing amount of basic compound is added and the admixture heated at 230260 F. (ll0-l27 C.). I

It is apparent that the preceding references contain contrariwise teachings in that US. Pat. No. 2,788,325 teaches substantially anhydrous conditions while US. Pat. No. 2,808,377 teaches the use of a small amount of water.

With regard to the aforementioned patents an important feature of the process of the present invention is that from about 1 to about 2.5 moles of water, per mole of dispersed basic alkaline earth metal compound in the product, must be present prior to the addition of any of the alkaline earth metal. I

In addition to the forementioned U.S. Patents, the prior art search uncovered the following US. Pat. Nos.: Re 26,811; 2,680,096; 3,321,399; 3,336,224;

c. adding to the admixture of step (b) a neutralizing amount of magnesium, calcium or barium in a glycol ether at a temperature higher than that of step (b) and in the range of about 55 to about C., and

d. removing the volatile materials by heating. The important features of the process are:

Ladding the overbasing amount of magnesium, calcium or barium prior to adding the neutralizing amount of magnesium, calcium or barium,

' 2. adding the overbasing amount of magnesium, calcium, or barium at a temperature below that used in adding the neutralizing amount of these materials, and r 3. having from 1.0 to 2.5 moles of water, per mole of dispersed magnesium, calcium or barium basic compound present in the final product, present in the admixture prior to the addition of the magnesium, calcium or barium in the glycol ether.

DETAILED DESCRIPTION Materials Used Suitable alkylphenols for use in our process are represented by the formula:

wherein-R is a straight chain or branched chain, saturated or unsaturated, aliphatic hydrocarbon radical having from four to 30 carbon atoms, preferably from nine to 15 carbon atoms, and n is an integer having a value of l or 2. The total number of carbon atoms for the alkyl groups has a minimum value of 8 and a maximum value of 40. Thus, when n is l the minimum number of carbon atoms in R is 8.

Examples of suitable hydrocarbon radicals include alkyl radicals such as butyl, hexyl, octyl, nonyl, decyl, dodecyl, hexcdecyl, eicosyl, hexacosyl and triacontyl; radicals derived from petroleum hydrocarbons such as white oil, wax and olefin polymers (e.g. polypropylene and polybutylene).

Suitable sulfurized alkylphenols include those materials prepared by sulfurizing alkylphenols using any of the known methods. For example, it is known that sulfur monochloride can be used to prepare sulfurized alkylphenols. Such a method is described in US. Pat. No. 2,409,687. The sulfurized alkylphenols which are suitable in our process can be illustrated by materials represented by the following formula:

OH OH gengmm R(n) wherein m is a number in the range of 1 to 3, more usually in the range of l to 2, and R and n are as described in the preceding description of the alkylphenols. It is to be understood that the preceding description is typical of the sulfurized alkylphenols which can be used and that our process is not limited to materials having the formula shown in the foregoing.

Regardless of the manner in which they are prepared the sulfurized alkylphenols which are useful in our process suitably contain from about 2 to about 14 percent by weight sulfur. Preferably, the amount of sulfur is from about 4 to about 12 percent by weight.

A wide variety of nonvolatile diluent oils are suitable in the process of our invention since the principle requisites for these materials are that they function as a solvent for the alkylphenate or sulfurized alkylphenate and serve to reduce the viscosity of the final product mixture. Often a small amount of the nonvolatile diluent oil is present in conjunction with the alkylphenol or sulfurized alkylphenol used in the process. The nonvolatile diluent oils have a boiling point in excess of about 200 C.

Examples of suitable nonvolatile diluent oils which can be used include mineral lubricating oils obtained by conventional refining procedures, synthetic lubricating oils such as polymers or propylene, polyoxyalkalenes, polyoxypropylene; dicarboxylic acid esters, and esters of acids or phosphorus; synthetic hydrocarbon lubricating oils, such as di-n-alkylbenzenes and oligomers of C -C alpha-olefins; vegetable oils, such as corn oil, cottonseed oil, and castor oil; animal oils, such as lard oil and sperm oil. Mixtures of these materials can also be employed as the nonvolatile diluent.

Of the preceding examples of nonvolatile diluent oils the mineral lubricating oils and the synthetic lubricating oils are considered more suitable, with the mineral lubricating oils being preferred.

Suitable process solvents for use in our process have a boiling point below about 150 C. Examples of suitable volatile process solvents include aromatic hydrocarbons, such as benzene, toluene, xylene, aliphatic hydrocarbons, such as hexane, heptane, petroleum naphtha, glycol ethers, as defined hereinafter, and primary aliphatic C,C alcohols.

The suitable alkaline earth metals, both for neutralizing the alkylphenol or sulfurized alkylphenol and for forming the dispersed basic compound, are magnesium, calcium or barium. Of these materials calcium and magnesium are considered more suitable, with.

magnesium being preferred.

In conducting the process of our invention a solution of the desired metal in a glycol ether is used. Suitable glycol ethers for use in our process include monoethers of ethylene glycol and monoethers of diethylene glycol containing up to eight carbon atoms. Preferred glycol ethers are the monoethyl ether of ethylene glycol and the monomethyl ether of ethylene glycol. These materials are available commercially under the trademarks Cellosolve and methyl Cellosolve. The monomethyl ether of diethylene glycol is available commercially under the trademark Carbitol.

The monoethers of ethylene glycol are also known as alkoxy alkanols, and more specifically as alkoxy ethanols. These materials have the generic formula ROCH,CH,OH

where R is a C, to C alkyl group. Similarly, the monoether of diethylene glycol has the generic formula HOCH,CH,OCH,CH,OR, where R is a C to C alkyl group.

As indicated in the foregoing, the metal used in the process is present as a solution in the suitable glycol ether. In some cases it may be desirable to use a carbonated metal alkoxide. The preparation of a calcium alkoxide-carbonate in an alkoxy alkanol solvent is described in U.S. Pat. No. 3,150,088. Similarly, the preparation of the magnesium analog is described in U.S. Pat. No. 3,150,089. The glycol ether solution of the metal contains from about 1 to about 30 weight percent, preferably from about 5 to about 25 weight percent of the metal. 0

The water requirements of the process of our invention can be met using water per se or a glycol etherwater mixture.

In some instances it is desirable to use a small amount of an oil-soluble sulfonic acid in the process of our invention. We have found that use of such a material results in certain improved properties of the product. For example, the B. S. and W., which is a measure of the amount of sediment on dilution, is improved. When used, preferably, the amount of oil-soluble sulfonic acid is from about 0.1 to about 50 parts per parts of alkylphenol or sulfurized alkylphenol.

When using the oil-soluble sulfonic acid preferably a volatile hydrocarbon solvent (elg. hexane) containing the oil-soluble sulfonic acid is used. The term oilsoluble sulfonic acid is well known in the art. In general, it refers to materials wherein the hydrocarbon portion of the molecule has a molecular weight in the range of about 300 to about 1,000, preferably in the range of about 370 to about 700.

Particularly suitable oil-soluble sulfonic acids are those prepared from various synthetic hydrocarbon sulfonation feedstocks. These materials are usually alkylbenzenes being either monoor dialkyl substituted. The alkyl groups have sufficient carbon atoms to attain the requisite molecular weight range described in the foregoing.

While the term oil-soluble sulfonic acid is believed to be very well understood in the art, in order to make my disclosure even more complete U.S. Pat. No. 3,525,599, to Gerald L. Nield, is made a part of this disclosure.

The amounts of the various materials used in our process when the metal is magnesium, calcium or barium, both suitable and preferred ranges, are shown below in parts by weight.

Suitable Preferred Alkylphenol or sulfurized alkylphenol 3-80 6-70 Volatile process solvent 0.S-250 1.0-100.0 Nonvolatile diluent oil 0.l0-95.00 5.0-90.0 Water 02044.00 03040.00

Glycol ether solution of magnesium, calcium, or

ban'um, containing:

Magnesium, calcium or barium 0.40-5000' 0.80-4000 Glycol ether 2.0-5000 3.0-800 Such a broad range is due to the difi'erence in atomic weights for magnesium and barium.

When the metal is magnesium the amounts of the various materials used in our process, both suitable and preferred ranges, are shown below in parts by weight.

Suitable Preferred Alkylphenol or sulfurized alk lphenol 4-80 9-70 Vo atile process solvent 0.5-200 2-80 Nonvolatile diluent oil lS-95 20-90 Water 0.20l4.0 0.30-l0.00 Glycol ether solution of magnesium containing: Magnesium 0.40l0.0 0.8-9.0 Glycol ether 2.0-1000 3.0200.0

PROCESS CONDITIONS In conducting the process of our invention, there is first formed an admixture, in a suitable reaction vessel of the alkylphenol or sulfurized alkylphenol, nonvolatile diluent oil, volatile process solvent and water. In those cases where it is desired to use an oil-soluble sulfonic acid, this material is added to the admixture at this point.

As indicated previously an important feature of our process is that the total water requirement is added prior to the addition of any alkaline earth metal. In view of this, the water is added to the initial admixture.

To the initial admixture there is then added an overbasing amount (from about 0.10 to 5 equivalents per equivalent of alkylphenol or sulfurized alkylphenol) of alkaline earth metal in a glycol ether. The overbasing amount of the alkaline earth metal in the glycol ether is added while maintaining the temperature of the admixture in the range of about to about 55 C. While the time of adding the overbasing amount of the alkaline earth metal in a glycol ether is not particularly critical, it is desirable that this addition occurs in a time period of from about 5 to about 120 minutes, preferably from about 30 to about 90 minutes. In this connection it is our hypothesis that since neutralization of alkylphenols requires higher temperatures that no, or at least very little, neutralization of the alkylphenol occurs under the conditions under which this step is conducted.

When it is desired that the dispersoid alkaline earth metal basic compound be a hydroxide, it is desirable to use in this first step a glycol ether solution of the suitable alkaline earth metal compound. In those cases where it is desired that the dispersoid alkaline earth metal basic compound be a carbonate, it is desirable to use a glycol ether solution of the alkaline earth metal alkoxide-carbonate complex. I

A neutralizing amount of the desired alkaline ea metal in a glycol ether is then added to the admixture. Preferably, this step is conducted while maintaining the temperature higher than in the overbasing step and in the range of about 55 to about 100 C. In order to complete the neutralization reaction it may be desirable to reflux the admixture at this point for a short time (e.g., 5 to 60 minutes).

The admixture is then heated to a suitable temperature (e.g., about 150 C.) to remove the volatile materials. If it is desirable that the dispersoid material be an alkaline earth metal carbonate, the admixture can be blown with CO during the final heating step. Blowingwith CO at this point serves to substantially complete the carbonation of the alkaline earth metal compound and to remove traces of volatile materials.

If necessary in order to bring the contents of the final product to the desired activity (i.e., concentration of alkylphenate and dispersoid material), an additional amount of a nonvolatile diluent oil can be added at this point.

MANNER OF DEFINING DISPERSED METAL CONTENT OF PRODUCTS OF OUR PROCESS Two methods of stating the amount of dispersed metal compounds are generally used in this field. One method states the dispersed metal compound as the base number" which refers to milligrams of potassium hydroxide per gram of sample. Preferably the base number is an acetic base number referring to an acetic acid titration method which utilizes glacial acetic acid and a solution of perchloric acid in glacial acetic acid as the titrant.

A second method uses the term metal ratio which is defined as the ratio of excess equivalents of metal in the composition to the equivalents of metal theoretically combinable as a normal salt with the alkylphenol or sulfurized alkylphenol. 1

Inasmuch as the neutral phenate or sulfurized neutral phenate titrates with the perchloric acid, this method has meaning only when the activity (i.e., amount of neutral phenate) is stated. (This statement does not apply to overbased sulfonates.) For the following reason the metal ratio method is preferred. 0

The products of our invention suitably have a metal ratio in the range of about 0.05 to about 5.0, preferably in the range of about 0.4 to about 2.0.

In order to disclose the nature of the present invention still more clearly, the following examples, both illustrative and comparative, will be given. It is to be understood that the invention is not to be limited to these specific conditions or detail set forth in these examples except insofar as such limitations are specified in the appended claims. Unless stated otherwise, the amounts of materials are stated as parts by weight.

EXAMPLE I This example illustrates the preparation of a dispersion of magnesium carbonate in a magnesium alkylphenate.

parts Materials Used:

Alkylphenol I40 n-l-lexane Water" 4.5 Methoxy ethanol solution of magnesium ethoxyethoxide-carbonate complex 'lhis alkylphenol contained about 92.5 weight percent C monoalkylphenol and about 7.5 weight percent free oil.

" The water was present in a water/methoxy ethanol azeotrope containing 50 percent water. This material contained 7.6 percent magnesium.

riod of about minutes while maintaining the temperature of the admixture at 4754 C. The admixture was then heated to reflux temperature (65-75 C.) and a second 80 part portion of the methoxy ethanol solution of the magnesium methoxy-ethoxide-carbonate complex was added over a period of about minutes. The admixture was then heated at reflux for an additional hour. At this point the solvents were removed by heating to 150 C. while blowing with CO gas. During this period 71 parts of 80 pale oil were added to adjust the concentration of the product.

The product had a very slight haze which was easily removed by filtering through a filter funnel precoated with Hyflo (a diatomaceous earth filter acid). The product had an acetic base number of 236 (theoretical 225) and a metal ratio of 1.03.

EXAMPLE 2 This example illustrates the preparation of a dispersion of magnesium carbonate in a magnesium salt of a sulfurized alkylphenate.

Materials Used: Parts Sulfurized alkylphenol 281.9 n-l-lexane 100 Water" 4.5 Methoxy ethanol solution of magrgesium methoxy-methoxidecar nate complex" 160 This material contained 50 percent diluent oil (80 pale oil, which is a distillate lubricating oil from Mid-Continent crude and has a viscosity of 80 S.S.U. at 100F.) and 50 percent sulfurized alkylphenol. The sulfurized alkylphenol was prepared from a mixture of 75 percent monononylphenol and percent dinonylphenol and contained 5.63 weight percent sulfur.

' Same as in Example 1.

'" Same as in Example 1.

Process:

The procedure employed was identical with that used in Example 1 with the exception of not adding the pale oil after stripping.

The product was a bright, clear, oi1-soluble material having an acetic base number of 175 (theoretical 180) and a metal ratio of 0.88.

EXAMPLE 3 This example illustrates the preparation of a dispersion of magnesium carbonate in a magnesium alkylphenate.

Materials Used: Parts Alkylphenol 150 mHexane 100 Water" 15 Hexane solution of sulfonic acid'" 14 Methoxy ethanol solution of nesium ethoxy-ethoxidenate complex" 282 Same as in Example 1.

*' Same as in Example 1.

The feedstock used to prepare this sulfonic acid was the same as that used in Example 4. The hexane solution had the following analysis:

Combining weight (as acid) 500 Sulfonic acid acidity, meqJg. 0.499 Nonvolatiles, weight percent 42.5 Oil, weight percent 17.6

"""" This material was an admixture of 70 grams of methoxy ethanol and 212 grams of a methoxy ethanol solution of magnesium methoxy ethoxide-carbonate complex containing 7.6 percent calcium.

Process:

To a 1-liter, 3-neck flask were added the alkylphenol, n-hexane, water-methoxy ethanol azeotrope and hexane solution of sulfonic acid. While stirring the admixture the methoxy ethanol solution of mangesium intermediate was added. 63 percent of the methoxy ethanol solution was added while maintaining the temperature in the range of 25 to 55 C. over a time period of 55 minutes. The remaining 37 percent of the me thoxy ethanol solution was added over a time period of 65 minutes while maintaining the admixture at reflux temperature condition (-73 C.).

Following the completion of the addition of the methoxy ethanol solution the admixture was heated at reflux for an additional hour. The solvents were then removed by heating to 150 C. while concurrently blowing with CO gas. During the solvent removal parts of 80 pale oil were added.

The product had an acetic base number of 251 (theoretical 250) and a metal ratio of 1.49.

EXAMPLE 4 This example illustrates the preparation of a dispersion of magnesium carbonate in a magnesium alkylphenate. It differs from Example 3 primarily in that a different type of alkylphenate was used.

Materials Used: Parts Alltylphenol" 1961 n-Hexane 1471 Methoxy ethanol 400 Hexane solution of sulfonic acid" 161 Water 75 Methoxy ethanol solution of magnesium methoxy-ethoxidecarbonate complex 1914 (1) This alkylphenol contained approximately 60 weight percent C, mono-alkylphenol, approximately 34 percent C,-dialky1pheno1, and approximately 6 percent free oil.

(2) The feedstock used to prepare this sulfonic acid wm an alkylbenzene prepared by alkylating benzene with an a-olefin mixture, wherein the olefins contained over 20 carbon atoms and were predominantly straight-chain. The acid had the following analysis:

Combining weight (as acid) 488 Sulfonic acid acidity, meq./g. 0.587 Nonvolatiles, weight percent 39.1 Oil, weight percent 10.45

(3) This material contained 7.48 weight percent magnesium.

Process:

To a l2-liter, 3-neck flask were added the alkylphenol, n-hexane, hexane solution of sulfonic acid, me thoxy ethanol and water. The admixture was heated to about 50 C. While maintaining the temperature of the admixture in the range of 49.5 to 53 C., 957 grams (one-half the total amount) was added in a 45 minute period. The admixture was then heated to reflux temperature and while maintaining the temperature in the range of 667 1 C., 7 grams of the methoxy ethanol solution of magnesium methoxy ethoxide carbonate complex was added over a period of 90 minutes. Upon completion of the addition of the methoxy ethanol solution of magnesium compound the admixture was heated to 150 C. at which point 900 grams of a naphthenic lubricating oil having a viscosity of 300 SSU at F. was added. The admixture was heated at a temperature of to C. for one hour to remove the solvents. During this time, the admixture was blown with CO, gas. The product while still hot was filtered through a filter funnel employing Hyflo diatomaceous earth. The yield of product was 3,150 parts having the following analysis and properties:

Metal ratio 0.67 B. S. & W., percent 0.25 Acetic base number 221 Magnesium, percent 4.88 Skinning tendency (24 hours) Very light This test is a measure of sediment formed on dilution of the product in a solvent. It is a standard test. 7

EXAMPLE This example illustrates the preparation of a dispersion of magnesium carbonate in a sulfurizedalkylphe- 60 rcent alkylbenzenes as described in Example 4 and'40 percent of a dr-n-alkylbenzene. The material had the following analysis:

Combining weight (as acid) 466 Sulfonic acidity, meqJg. 0.559

Nonvolatiles, weight percent 32.85

Oil, weight percent (4) 1.2 mole of water per mole of overbasing'magnesium employed. 5) This material was a methoxy ethanol solution of methoxy ethoxidecarbonate complex containing 7.98 percent magnesium.

Process:

To a 12-liter, 3-neck flask were added the sulfurized alkylphenol, hexane, methoxy ethanol, naphthenic lubricating oil, hexane solution of sulfonic acid and water. While mixing the materials and maintaining the temperature in the range of 25-55 C., 941 grams of the carbonated magnesium intermediate was added over a 60 minute period. The admixture was then heated to reflux temperature and while maintaining the admixture at a temperature of 6776 C., 941 grams of the carbonated magnesium intermediate were added over a period of 60 minutes. The volatile materials were then removed from the admixture by heating it to 150 C. The admixture was maintained at a temperature in the range of 140-l 60 C. for 1 hour while blowing with CO Twenty grams of the naphthenic lubricating oil were added to adjust the total product weight to 2,750 grams. The final product had the following analysis and properties:

Sulfur, weight EXAMPLE 6 This example illustrates the preparation of a dispersion of calcium carbonate in a sulfurized alkylphenol.

10 Materials Used: Parts sulfurized alkylphenol Hexane 84 Methoxy ethanol 20 Naphthenic lubricating oil 16.8 Hexane solution of sulfonic acid" 7.9 Water 3.67 Calcium intennediate 157.2

(1) This material contained. a mixture of sulfurized mono-C and di- C alkylphenols. It contained 73.6 percent sulfurized phenols and 26.4 percent free oil. The material contained 6.1 1 weight percent sulfur-and 0.80 weight percent chlorine-The material was stripped with an inert gas to remove impurities prior to using.

(2) Same as in Example 5.

(3) This material was prepared by sulfonation of a complex mixture of hydrocarbons. It contained some long chain monoalkylbenzenes and some di-n-alkylbenzenes. The material had the following analysis:

Oil, weight percent (4) 1.2 moles of water per mole of overbasing calcium. (5) The calcium intennediate was a methoxy ethanol solution of cal cium methoxy ethoxide-carbonate complex containing 7.42 weight percent calcium.

PROCESS To a Pfaudler reaction vessel were added the sulfurizedf alkylphenol, hexane, methoxy ethanol, naphthenic lubricating oil, hexane solution of sulfonic acid, and water. To this admixture there was added 78.6 pounds (one-half of the total amount shown above) of the calcium intermediate. The calcium intermediate was added over a period of 60 minutes while maintaining the temperature in the range of 24-58 C. The admixture was then heated to reflux temperature (75-78 C.). While maintaining the admixture at this temperature 78.6 pounds (the remainder of the total amount) of the calcium intermediate was added over a time period of 60 minutes. Following the addition of the calcium intermediate the admixture was heated over a period of 3 hours to a final temperature of 150 C. to remove solvents. During the final one hour and 10 minutes of this heating period the admixture was blown with CO gas. The product, after filtering, had the following analysis and properties:

Metal ratio 1.43 Acetic base number 230 Viscosity at 210F., cs. 245.8 B S. & W 0.055 Calcium, 8.29 Sulfur, 4.50 Skinning Tendency nil EXAMPLE 7 This example illustrates the preparation of a dispersion of calcium hydroxide in a calcium salt of a sulfurized alkylphenol wherein the product contained 40 percent (weight) of dispersant.

Materials Used: Parts sulfurized alkylphenol" 186.6 n-Hexane Methoxy ethanol 60 Naphthenic lubricatin oil" 121.3 Hexane solution of s onic acid" 19.0 Water 5.2 Methoxy ethanol solution of calcium 251.2

(1) This material was a sulfurized mixture of monononylphenol and dinonylphenols, having the following analysis:

Oil, wt. 11 26.4 Phenols, wt. 73.6 Average equavalent weight of sulfurized phenols Sulfur, wt.

Combining weight (as acid) 503 Sulfonic acid acidity, meq./g. 0.529 Nonvolatiles, weight percent 28.8 Oil, weight percent 2.3

(4) This amounted to 1.3 moles of water per mole of dispersed phase. Containing 7.02% Ca Process:

The procedure was substantially the same as shown in Example 3, except that the product was stripped with nitrogen gas at l40-160 C. for one hour.

The overbasing amount (firs additon) of methoxy ethanol solution of calcium was 117.5 grams. It was added over a period of 30 minutes at a temperature of 25.5 to 52 C.

The neutralizing amount (second addition) of methoxy ethanol solution of calcium was 133.7 grams. It was added over a period of 45 minutes at a temperature of 75.5-77.5 C.

The yield of product was 352.3 grams. The product had the following analyses and properties:

Acetic base number 134 Metal ratio 0.77 Calcium, wt. 5.10 Sulfur, wt. 3.69 Viscosity at 210F., cs. .1

B. S. & W., (unfiltered) 0.65

EXAMPLE 8 This example illustrates the preparation of a dispersion of magnesium hydroxide in a magnesium salt of a sulfurized alkylphenol wherein the product contained 55 percent (weight) of dispersant.

Materials Used: Parts Sulfurized alkylphenol" 264.0 Benzene 120 Methoxy ethanol 120 Naphthenic lubricating oil 46.0 Hexane solution of sulfonic acid 19.3 Water" 6.4 Methoxy ethanol solution of magnesrum 166.3

(1) Same as in Example 7.

(2) Same as in Example 5.

(3) Same as in Example 7.

(4) This amounted to 1.3 moles of water per mole of dispersed phase. (5) containing 8.86 percent magnesium.

Process:

The procedure was substantially the same as in Example 3 except that the product was stripped with nitrogen gas at l40-160 C. for 1 hour.

The overbasing amount (first addition) of methoxy solution of magnesium was 72.7 grams. It was added over a period 30 minutes at a temperature of 250 to 510 C.

The neutralizing amount (second addition) of methoxy ethanol solution of magnesium was 93.6 grams. It was added over a period of 45 minutes at a temperature of 80-92.5 C.

The yield of product was 355.7 grams. The product had the following analyses and properties:

Acetic base number 189 Metal ratio 0.77 Magnesium, wt. 4.29 Sulfur, wt. 5.14 Viscosity at 210F., cs. 1 140.9

(unfiltered) 0.30

EXAMPLE 9 This example illustrates the preparation of a dispersion of magnesium carbonate in a magnesium salt of a sulfurized alkylphenol containing 50 percent (weight) of dispersant.

Materials Used: Parts Sulfurized alkylphenol" 240.0 n-Hexane 120 Methoxy ethanol 60 Naphthenic lubricating oil" 80.0 Water" 3.3 Methoxy ethanol solution of magnesium alkoxide-carbonate complex" 142.6

(1) Same as in Example 7.

(2) Same as in Example 5.

('3) This amounted to 1.2 moles of water per mole of dispersed phase. (4) Containing 7.98 percent magnesium.

Process:

The procedure was substantially the same as shown in Examples 4-6, except that no sulfonic acid was used.

The overbasing amount (first addition) of methoxy ethanol solution of magnesium alkoxide-carbonate complex was 46.0 grams. It was added over a period of 30 minutes at a temperature of 26.5 to 55 C.

The neutralizing amount (second addition) of methoxy ethanol solution of magnesium alkoxidecarbonate complex was 96.6 grams. It was added over a period of 45 minutes at a temperature of 74 to 78 C.

The yield of product was 346.9 grams. The product had the following analyses and properties:

Acetic base number 149 Metal ratio 0.8 M sium, wt. k 3.33 Su wt. 4.53 Viscosity at 2l0"F., cs. 207.6 B. S. & W.

(unfiltered) 0.65

The invention having thus been described, what is claimed and desired to be secured by Letters Patent is: 1. A process for preparing highly basic magnesium, calcium or barium salts of alkylphenols or sulfurized alkylphenols, wherein the process comprises:

a. forming an admixture of i. about 3 to about 80 parts by weight of an alkylphenol or a sulfurized alkylphenol, wherein the alkylphenol is represented by the formula wherein R is a straight or branched chain, saturated or unsaturated, aliphatic hydrocarbon radical having from four to 30 carbon atoms, and n is an integer, having a value of l or 2, said alkylphenol being characterized further in that the total number of carbon atoms in the alkyl group or groups is from 8 to 40,

ii. from 0.10 to 95 parts by weight of a nonvolatile diluent oil having a boiling point in excess of about 200 C.,

iii. from 0.5 to 250 parts by weight of a volatile process solvent having a boiling point below about 150 C., and

iv. from 0.2 to 14 parts by weight water;

b. while the temperature is in the range of about 20 to about 55 C., adding to the admixture of step (a) an overbasing amount of a glycol'ether solution of magnesium, calcium or barium, said glycol ether being selected from the group consisting of materials represented by the formula ROCH CH OH wherein R is a C to C alkyl group and materials represented by the formula HOCH CH OCH CH OR where R is a C to C alkyl group;

c. while maintaining theadmixture at a temperature higher than in step (b) and in the range of about 55 to about 100 C. adding thereto a neutralizing amount of a glycol ether solution of magnesium, calcium or barium, wherein i. the cation is the same as in step (b), and ii. the glycol ether is as defined in step (b); and

d. removing the volatile materials by heating, said process being characterized further in that i. the overbasing amount of glycol ether solution of magnesium, calcium or barium is from about 0.1 to about 5 equivalents of metal per equivalent of alkylphenol or sulfurized alkylphenol,

ii. the total amount of magnesium, calcium or barium in the glycol ether solution added in the process is from about 0.4 to about 50 parts by weight, and

iii. the amount of water in step (a) (iv) is sufficient to provide 1.0 to 2.5 moles per mole of dispersed magnesium, calcium or barium.

2. The process of claim 1 wherein the non-volatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricatingoils.

3. The process of claim 2 wherein the process solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, primary aliphatic C -C, alcohols and C, to C glycol ethers.

4. The process of claim 3 wherein the glycol ether used to prepare the glycol ether solution of magnesium, calcium or barium is monomethyl ether of ethylene glycol or monoethyl ether of ethylene glycol.

5. The process of claim 4 wherein the amounts of materials in step (a) are:

parts by weight about 6 to about 70 about 5 to about 90 about l to'about I00 about 0.3 to about 10 (i) alkylphenol or sulfurized alkyl henol (ii) nonvolatile cluent (iii) volatile process solvent (iv) water 6. The process of claim 5 wherein the metal is magnesium or calcium.

7. The process of claim 6 wherein the process solvent 8. The process of claim 7 wherein the process solvent is a mixture of hexane and methoxy ethanol.

9. The process of claim 8 wherein the nonvolatile diluent oil is a mineral lubricating oil.

10. The process of claim 6 wherein the process solvent is a mixture of an aromatic hydrocarbon and a C to C glycol ether.

11. The process of claim 10 wherein the process solvent is a mixture of benzene and methoxy ethanol.

12. The process of claim 11 wherein the nonvolatile diluent oil is a mineral lubricating oil.

13. The process of claim lwherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.

14. The process of claim 5 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.

15. The process of claim 9 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.

16. The process of claim 12 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.

17. A process for preparing a highly basic magnesium salt or alkylphenols and sulfurized alkylphenols wherein the process comprises:

a. forming an admixture of i. about 4 to about parts by weight of an alkylphenol or a sulfurized alkylphenol wherein the alkylphenol is represented by the formula wherein R is a straight chain or branched chain, saturated or unsaturated, aliphatic hydrocarbon radical having from four to 30 carbon atoms, and

g n is an integer, having a value of l or 2, said alkylphenolbeing characterized further in that the total number of carbon atoms in the alkyl group or groups is from 8 to 40,

ii. about 15 to about parts by weight of a nonvolatile diluent oil having a boiling point in excess of about 200 C.,

iii. about 0.5 to about 250 parts by weight of a volatile process solvent having a boiling point below about 150 C., and

iv. about 0.2 to about 14 parts by weight water;

b. while the temperature is in the range of about 20 to about 55 C. adding to the admixture of step (a) an overbasing amount of a glycol ether solution of magnesium, said glycol ether being represented by the formula ROCH,CH,OH

wherein R is a C to C, alkyl group;

c. while maintaining the admixture at a temperature higher than in step (b) and in the range of about 55 to about C. adding thereto a neutralizing amount of a glycol ether solution of magnesium wherein the glycol ether is as defined in step (b); and

d. removing the volatile materials by heating, said process being characterized further in that i. the overbasing amount of glycol ether soltuion of magnesium is from about 0.1 to about equivalents of magnesium per equivalent of alkylphenol or sulfurized alkylphenol,

ii. the total amount of magnesium in the glycol ether solution added in the process is from about 0.4 to about parts by weight, and

iii. the amount of water in step (a) (iv) is suflicient to provide 1.0 to 2.5 moles per mole of dispersed magnesium, calcium or barium.

18. The process of claim 17 wherein the nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.

19. The process of claim 18 wherein the process solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, primary aliphatic C,-C alcohols, and C;, to C glycol ethers.

20. The process of claim 19 wherein the glycol ether is monomethyl ether of ethylene glycol.

21. The process of claim 17 wherein the amounts of materials in step (a) are parts by weight about 9 to about 70 about 20 to about 90 diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.

23. The process of claim 22 wherein the process solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, primary aliphatic C,C, alcohols and C to C glycol ethers.

24. The process of claim 23 wherein the process solvent is a mixture of an aliphatic hydrocarbon and a C to C, glycol ether.

25. The process of claim 24 wherein the process solvent is a mixture of hexane and methoxy ethanol.

26. The process of claim 25 wherein the nonvolatile diluent oil is a mineral lubricating oil.

27. The process of claim 23 wherein the process solvent is a mixture of an aromatic hydrocarbon and a C to C glycol ether.

28. The process of claim 27 wherein the process solvent is a mixture of benzene and methoxy ethanol.

29. The process of claim 28 wherein the nonvolatile diluent oil is a mineral lubricating oil.

30. The process of claim 17 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per parts of alkylphenol or sulfurized alkylphenol.

31. The process of claim 26 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.

32. The process of claim 29 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol. 

2. The process of claim 1 wherein the non-volatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
 3. The process of claim 2 wherein the process solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, primary aliphatic C1-C6 alcohols and C3 to C8 glycol ethers.
 4. The process of claim 3 wherein the glycol ether used to prepare the glycol ether solution of magnesium, calcium or barium is monomethyl ether of ethylene glycol or monoethyl ether of ethylene glycol.
 5. The process of claim 4 wherein the amounts of materials in step (a) are: parts by weight (i) alkylphenol or sulfurized alkylphenol about 6 to about 70 (ii) nonvolatile diluent about 5 to about 90 (iii) volatile process solvent about 1 to about 100 (iv) water about 0.3 to about 10
 6. The process of claim 5 wherein the metal is magnesium or calcium.
 7. The process of claim 6 wherein the process solvent is a mixture of an aliphatic hydrocarbon and a C3 to C8 glycol ether.
 8. The process of claim 7 wherein the process solvent is a mixture of hexane and methoxy ethanol.
 9. The process of claim 8 wherein the nonvolatile diluent oil is a mineral lubricating oil.
 10. The process of claim 6 wherein the process solvent is a mixture of an aromatic hydrocarbon and a C3 to C8 glycol ether.
 11. The process of claim 10 wherein the process solvent is a mixture of benzene and methoxy ethanol.
 12. The process of claim 11 wherein the nonvolatile diluent oil is a mineral lubricating oil.
 13. The process of claim 1 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
 14. The process of claim 5 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
 15. The process of claim 9 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
 16. The process of claim 12 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
 17. A process for preparing a highly basic magnesium salt or alkylphenols and sulfurized alkylphenols wherein the process comprises: a. forming an admixture of i. about 4 to about 80 parts by weight of an alkylphenol or a sulfurized alkylphenol wherein the alkylphenol is represented by the formula
 18. The process of claim 17 wherein the nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
 19. The process of claim 18 wherein the process solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, primary aliphatic C1-C6 alcohols, and C3 to C8 glycol ethers.
 20. The process of claim 19 wherein the glycol ether is monomethyl ether of ethylene glycol.
 21. The process of claim 17 wherein the amounts of materials in step (a) are parts by weight (i) alkylphenol or sulfurized alkylphenol about 9 to about 70 (ii) nonvolatile diluent oil about 20 to about 90 (iii) volatile process solvent about 2 to about 80 (iv) water about 0.3 to about 10
 22. The process of claim 21 wherein the nonvolatile diluent oil is selected from the group consisting of mineral lubricating oils and synthetic lubricating oils.
 23. The process of claim 22 wherein the process solvent is selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, primary aliphatic C1-C6 alcohols and C3 to C8 glycol ethers.
 24. The process of claim 23 wherein the process solvent is a mixture of an aliphatic hydrocarbon and a C3 to C8 glycol ether.
 25. The process of claim 24 wherein the process solvent is a mixture of hexane and methoxy ethanol.
 26. The process of claim 25 wherein the nonvolatile diluent oil is a mineral lubricating oil.
 27. The process of claim 23 wherein the process solvent is a mixture of an aromatic hydrocarbon and a C3 to C8 glycol ether.
 28. The process of claim 27 wherein the process solvent is a mixture of benzene and methoxy ethanol.
 29. The process of claim 28 wherein the nonvolatile diluent oil is a mineral lubricating oil.
 30. The process of claim 17 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
 31. The process of claim 26 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol.
 32. The process of claim 29 wherein the admixture of step (a) contains additionally from about 0.1 to about 50 parts of oil-soluble sulfonic acid per 100 parts of alkylphenol or sulfurized alkylphenol. 